Alkylene ethers of thioammeline



Patented Dec. 31, 1940 a I UNITED STATES PATENT OFFICE 2,227,215 snxrnsm: n'rnans or rmoammrms Herman a. Brnson. Philadelphia, la., assi nor to The Delirious Products a: Chemical Company,

Philadelphia, Pa.

No Drawing. Application March 13, 1940,

7 Serial No. 323,725

7 Claims. (01. 260-248) This invention relates to new thioammeline hols, of phenols, and of merc-aptans. There may ethers having alkylene ether or polyalkylene ether be used, for example:

chains attached to thetriazine nucleus through OCHIC a sulfur linkage. Compounds of this type were disclosed in application Serial NO. 5

filed 11, of which the present application 18 a continuation-in-part. CHOCHzCHzCHzOCHCHzCHZCI It is an object of this invention to provide a cmscmcmcl simple, practical method of making these new CmCHwHDOCHCHCI 10 compounds. It 18 8150 an object 1'0 makeavail- 10 able new materials suitable for the production of Cmocmcmocmcmocmcmcl new resins and for the modification of carbamidem h d resins, t is a further object to and analogous higher homologues thereof, such vjde new products and intermediates not only f as the amyl, octyi, undecenyl, dodecyl, etc. chlororesin manufacture but also f r many agricultural, ethers. Furthermore, the corresponding aromatic pharmaceutical, and industrial products and hetemcyclic and hydroaromatic fioroalkyl uses. ethers such as the following may also be used:

According to the invention, thioanimeline is CTHsSCHZCHZCI 2o condensed in the presence of an alkaline, acid- LJH5OCHCHC1 binding agent with arylaliphatic, heterocycliccmsscmcmocmcmcl 20 aliphatic, alicyclicaliphatic, and aliphatic ether c'ig-"ocmcmrmmoclmfml halides possessing at least three carbon atoms. C OCHCHOCHCHOCHzCHzOCHzCHzCl CtI-ItOCHP-CHaCHaOCHaCHzCI hCI In the preferred form of this invention thioammeline is mixed with an aqueous or alcoholic cemcmocmcmcl solution or dispersion of an inorganic alkaline material, such as sodium hydroxide, and with an equivalent proportion of the ether halide. In some cases the reaction starts at room temperatures; in other cases heat is required. In either cm 30 case the reaction is accelerated by heating the mixture with rapid and efllcient stirring. It is cfl'yccwmmcmcmcl most convenient to heat the mixture under reflux CH; at I0-100 0., but higher temperatures may be N used if the heating is conducted under pressure. 35

The reaction may be accelerated by the presence 0 S E N N N of catalysts, such as potassium iodide or other B iodides,- or amines, such as pyridine. The product formed by the reaction usually separates in 0 m m m m i 40 crystalline form and can then be removed from 40 the reaction mixture by filtration (or other suitable method) and further purified, if desired. on, (memo cmcnio cmcmci Variations in thisgeneral procedure are, of

course, allowable. Thus, .the halide may be added m; r in steps or the order of the addition 5L? 45 0 components may be altered, but still with satisfactory 8mm rhc cnocmcmocmcnici e? $.12; illia 591%? usedanyo er ase,ora ne,ac

in: agent, such as potassium hydroxide, potas- Bomylwcmcmocmcmcl 50 sium carbonate, di carbonate, m barium Any aryl groups present in the ether halides hydroxide, zinc hydroxide; an th likecan be substituted nulcearly by halogen, alkyl,

e 1 6 halides'which are most useful for aryl, aralkyl, alkoxy, hydroxy, cycloalkyl,. nitro, preparing alkylene ether ammeline thioethers are acyi, or other suitable groups or radicals. In the p-halogeno-alkyl ethers of monohydric alcoplace of the chlorides shown there may be used wherein A is an alkylene group of .at least two carbon atoms, X represents at least one member of the group consisting of oxygen and sulfur, R

aryl groups, aralkyl groups, heterocyclic groups, and alicyclic and aliphatic hydrocarbon groups, and n is an integer from one to four.

The following examplesare illustrative of this 25 invention:

Example 1 A solution, consisting of 42.9 g. of thioammeline, 13.2 g. of sodium hydroxide, and 300 cc. of water, is mixed with 200 cc. of ethanol and 47 g. of B-chloroethoxybenzene, and boiled under reflux with rapid stirring for 15 hours. The crystalline product which separates is filtered off. After recrystallization from hot alcohol, it sepaas rates in colorless, fine crystals melting at 177 C.

and having the formula all? Example 3 65 To a clear solution of 21.5 g. of thioammeline,

6.6 g. of sodium hydroxide, 100 cc. of water and 100 cc. of ethanol there is added 41 g. of p-chloroethoxyethyl thiobenzothiazole ClCHzCHr-CH:CHx-SC 75 The mixture is stirred rapidly and'bolled under represents a member of the group consisting of Example 4 A clear solution of 42.9 g. of thioammeline, 13.2 g. of sodium hydroxide, and 300 cc. of water is mixed with 200 cc. of ethanol and 54.2 g. of butoxyethoxyethyl chloride,

and boiled under reflux for 24 hours while the reaction mixture is rapidly stirred. An oily layer forms which is separated from the aqueous layer, mixed with benzene, and washed with water. On standing, the benzene solution crystallizes. After recrystallization from benzene, the product is obtained in colorless crystals, M. P. 80 0., having the formula 7 To a clear solution of 42.9 g. of thioammeline, 13.2 g. of sodium hydroxide, and 300 cc. of water there is added a mixture of 200 cc. of ethanol and 60.2 g. of p-phenoxy-p'-chlorodiethyl ether. The mixture is stirred and boiled under reflux for 18 hours. The white, insoluble product which forms is filtered off, washed with water, alcohol, and dried. There is obtained 70 g. of white powder, which, upon recrystallization from boiling toluene, separates in fine, colorless needles, M. P. 76-77" 0., having the formula N\ N/ c-s--cmcn=-o-orncmo-otrn i NH: 1

Example 6 V To a clear solution of 21.5 g. of thioammeline, 6.6 g. of sodium hydroxide, 150 cc. of water, 100 cc. of ethanol and 0.5 cc. of pyridine there is added 16.3 g. offB-chloroethoxyethane. stirred and boiled under reflux for eight hours. The clear solution obtained deposits crystals on standing. The yield is 20 g. Onrecrystallization from water, the compound separates in colorless crystals, M. P. 148-149" 0., having the formula (LN N/ c-s-omcnro-onlonf \C=N l lfla Example 7 g The mixture is A solution of 21.5 g. of thioammeline, 6.6 g. of 7| formula C-S-CHgCHr-G-CILCHa-O c1 C=N 217B:

Ezample 8 On cooling. the white crystalline product obtained is filtered off, washed with water, then with alcohol and finally recrystallized from toluene. It separates "in colorless crystals, M. P. 148-149 0.. having the formula colorless crystals,

The compounds obtained according to this invention are useful alone or in the form of their salts as bactericides, insecticides, vulcanization accelerators, corrosion inhibitors, pickling inhibitors, additives for petroleum products, intermediates for textile assistants, dyes. drugs. etc. They may be condensed with aldehydes, such as formaldehyde, to form useful resins. They may also be used in conJunction with phenols, urea, thiourea, dicyandiamide, or other methylol-forming compounds for the formation of resins suitable for coating, casting, laminating. molding, or impregnating compositions. Resins formed therewith are of particular interest because of the increased alcohol tolerance resulting from the presence of the polyether linkages I I claim:

1. A method for preparing polyethers or thioammelin which comprises reacting in the presence of an alkaline, acid-binding agent thioamcarbon 2. A method for ammeilne, which WHrCHsO).

wherein n represents an integer from one to four inclusive.

5. A compound having the formula A-CHICHIO 8. A compound having the formula N mN-o 'JNHa E4:mcm-o-cmcm-o-cmcmcmcm 7. A compound having the formula HERMAN A. BRUSON. 

